JPH0324406B2 - - Google Patents
Info
- Publication number
- JPH0324406B2 JPH0324406B2 JP27207184A JP27207184A JPH0324406B2 JP H0324406 B2 JPH0324406 B2 JP H0324406B2 JP 27207184 A JP27207184 A JP 27207184A JP 27207184 A JP27207184 A JP 27207184A JP H0324406 B2 JPH0324406 B2 JP H0324406B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- caco
- reaction
- bones
- cahpo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 17
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Description
〔産業上の利用分野〕
本発明は、炭酸含有ヒドロキシアパタイトの製
造法に関する。
近年、人工骨、人工歯根の材料として種々のセ
ラミツクが用いられており、このうち、ヒドロキ
シアパタイトは、人間の歯・骨に組成、構造が非
常に似ているため生体内に埋入した場合安全かつ
化学的に安定であり、しかも生体拒否反応を起こ
すことなく自然骨と結合治瘉しやすいなどのこと
から、大いに注目されている材料である。
一方、生体内の骨や歯が炭酸を含有しているこ
とはよく知られている。従つてヒドロキシアパタ
イトを生体材料として用いる場合、生体に対する
なじみや、順化期間の短縮化、あるいは生体の拒
否反応を少なくするうえで、できる限り生体内の
骨や歯と組成的に近いヒドロキシアパタイトが要
求され、本発明はかかる材料の製造に関するもの
である。
〔従来の技術〕
ヒドロキシアパタイトの合成法としては、大気
圧下での水溶液反応による湿式法と高温下の固相
反応による乾式法の二つがある。しかしながら、
かかる湿式法においては、反応速度が遅く、かつ
得られる沈殿物がコロイド状となるために、取扱
いや操作に不便であり、また生成物の組成比がわ
ずかな反応条件の差によつても変化し、一定のも
のをうることが困難であるなどのために実用化さ
れるにはいたつていない。一方、乾式法において
も水蒸気分圧の存在下で1000℃以上の高温で長時
間の焼成が必要であり、かつ炭酸を含有したヒド
ロキシアパタイトをうることができないという欠
点がある。
〔発明が解決しようとする問題点〕
ヒドロキシアパタイトの湿式及び乾式による合成
法においては、生体内の骨や歯と同じ組成である
炭酸を含有したヒドロキシアパタイトをうること
ができない。
すなわち生体内の骨や歯が炭酸を含有している
ことは公知であり、そのため生体材料として用い
る場合、生体に対する親和性や順化期間の短縮
化、あるいは生体の拒否反応を少なくするうえ
で、できる限り生体内の骨や歯と組成的に近いヒ
ドロキシアパタイトを用いることが望ましい。
〔問題点を解決するための手段〕
本発明者らは、叙上の欠点を排除し、所望の炭
酸を含有したヒドロキシアパタイトをうるべく
種々研究を重ねた結果CaHPO4と水のスラリーに
CaCO32〜25mol％含有するCa（OH）2とCaCO3の
混合物をPH10以下に保ちながら徐々に加え60〜
100℃にて反応をおこなわせることにより、所望
の炭酸が含有されてなるヒドロキシアパタイト粉
末がきわめて短時間で容易に生成されうるという
新規製造法を見出し、本発明を完成するにいたつ
た。
すなわち、本発明の方法は、CaHPO4と水のス
ラリーにCaCO32〜25モル％含有するCa（OH）2と
CaCO3との混合物をPH10以下に保ちながら加え
60℃にて反応をおこなわせるもので、ここでの加
熱は反応時間を短縮させるためのものであり、ま
た、PH10以下に保つのは、反応を進行させるため
で、PH10以上になると、反応速度はきわめて遅く
なり、未反応のCaHPO4が残存し、ヒドロキシア
パタイトを単独で得ることが難しい。
更に、本発明の方法において、CaCO3を用い
るのは、炭酸を含んだヒドロキシアパタイトを得
るためであり、CaCO3含有量が大になればヒド
ロキシアパタイト中の炭酸含有量も増加する傾向
にある。CaCO3含有量を２〜25mol％に限定して
いるのは、ヒドロキシアパタイト中の炭酸量を人
間の歯や骨と同程度に制御するためで0.5〜3.6重
量％（CO2として）の範囲にすることができる。
また、本発明の方法において、CaHPO4原料に
対するCa（OH）2とCaCO3混合物の供給量は仕込
みのCa／Ｐモル比で1.62〜1.67にする必要があ
る。仕込みのCa／Ｐ比が1.67より大のときはCa
（OH）2またはCaCO3が、1.62より小のときは
CaHPO4がヒドロキシアパタイトに混在する。
また、Ca（OH）2とCaCO3の供給は粉の状態で
もよい。
またCaHPO4のかわりにCaHPO4・2H2Oを用
いることも勿論可能であるが反応条件によつては
一部リン酸８カルシウムが生成することもあるた
めCaHPO4の方が好ましい。
以下、実施例により、本発明をより詳細に説明
する。
実施例 1.2
温水ジヤケツトを施したSUS304製蓋つき60
反応装置に撹拌機、PH計、温度計、還流冷却器を
セツトし、内部にCaHPO4を水と共に仕込んだの
ち加温し、所定の温度となつた時点で別に設けた
撹拌機つきのCaCO310〜25mol％を含有するCa
（OH）2とCaCO3との混合タンクから温水ジヤケ
ツトにより予熱された10％のCa（OH）2＋CaCO3
混合液をポンプで反応装置に供給し、反応をおこ
なつた。反応終了後生成物を濾別し、水洗、乾燥
した。
反応条件および結果を第１表に示す。また実施
例１、２の各反応時間でのPH、Ca（OH）2＋
CaCO3の添加率の関係を第１図および第２図に
得られた生成物の赤外吸収スペクトルのパターン
を第３図および第４図に示す。
第３図および第４図ともに波数1400cm-1付近に
おいて炭酸に関連する特有な吸収を示しており、
炭酸を含有していることを確認した。
比較例 １
CaHPO4とCaCO3をボールミルで混合し、ルツ
ボに入れ、1000〜1100℃、水蒸気圧下の電気炉中
で５時間焼成した結果を第１に示す。
[Industrial Field of Application] The present invention relates to a method for producing carbonic acid-containing hydroxyapatite. In recent years, various ceramics have been used as materials for artificial bones and artificial tooth roots. Among these, hydroxyapatite is safe when implanted in living organisms because its composition and structure are very similar to human teeth and bones. It is a material that is attracting a lot of attention because it is chemically stable, and can be easily bonded to natural bone without causing biological rejection. On the other hand, it is well known that bones and teeth in living organisms contain carbonic acid. Therefore, when using hydroxyapatite as a biomaterial, it is important to use hydroxyapatite that is as close in composition to in-vivo bones and teeth as possible in order to be compatible with the living body, shorten the acclimatization period, and reduce rejection reactions by the living body. There is a need and the present invention relates to the manufacture of such materials. [Prior Art] There are two methods for synthesizing hydroxyapatite: a wet method using an aqueous solution reaction under atmospheric pressure, and a dry method using a solid phase reaction at high temperatures. however,
In such a wet method, the reaction rate is slow and the resulting precipitate is colloidal, making it inconvenient to handle and operate, and the composition ratio of the product changes even due to slight differences in reaction conditions. However, it has not yet been put into practical use because it is difficult to obtain a certain amount. On the other hand, the dry method also has the drawback that it requires long-term calcination at a high temperature of 1000° C. or higher in the presence of water vapor partial pressure, and that hydroxyapatite containing carbonate cannot be obtained. [Problems to be Solved by the Invention] In the wet and dry synthesis methods of hydroxyapatite, it is not possible to obtain hydroxyapatite containing carbonate, which has the same composition as bones and teeth in living bodies. In other words, it is well known that bones and teeth in living organisms contain carbonic acid, and therefore, when used as biomaterials, it is important to improve affinity with living organisms, shorten the acclimatization period, and reduce rejection reactions by living organisms. It is desirable to use hydroxyapatite, which is compositionally similar to in-vivo bones and teeth as much as possible. [Means for Solving the Problems] The present inventors have conducted various studies to eliminate the above-mentioned drawbacks and obtain hydroxyapatite containing desired carbonate, and as a result, they have developed a slurry of CaHPO 4 and water.
Gradually add a mixture of Ca(OH)2 and CaCO3 containing 2-25 mol% of CaCO3 while keeping the pH below 60~
We have discovered a new production method in which hydroxyapatite powder containing the desired carbonic acid can be easily produced in a very short time by carrying out the reaction at 100°C, and have completed the present invention. That is, the method of the present invention uses Ca(OH) 2 containing 2 to 25 mol% of CaCO 3 in a slurry of CaHPO 4 and water.
Add the mixture with CaCO 3 while keeping the pH below 10.
The reaction is carried out at 60℃, and the heating here is to shorten the reaction time.Also, keeping the pH below 10 is to allow the reaction to proceed, and when the pH exceeds 10, the reaction rate slows down. The process is extremely slow and unreacted CaHPO 4 remains, making it difficult to obtain hydroxyapatite alone. Furthermore, in the method of the present invention, CaCO 3 is used to obtain hydroxyapatite containing carbonate, and as the CaCO 3 content increases, the carbonate content in hydroxyapatite tends to increase as well. The reason why the CaCO 3 content is limited to 2 to 25 mol% is to control the amount of carbon dioxide in hydroxyapatite to the same level as human teeth and bones. can do. In addition, in the method of the present invention, the amount of the Ca(OH) 2 and CaCO 3 mixture supplied relative to the CaHPO 4 raw material needs to be set at a molar ratio of Ca/P of 1.62 to 1.67. When the Ca/P ratio of the preparation is greater than 1.67, Ca
When (OH) 2 or CaCO 3 is less than 1.62
CaHPO4 is mixed in hydroxyapatite. Further, Ca(OH) 2 and CaCO 3 may be supplied in powder form. It is of course possible to use CaHPO 4 .2H 2 O instead of CaHPO 4 , but CaHPO 4 is preferable because octacalcium phosphate may be partially produced depending on the reaction conditions. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1.2 60 with SUS304 lid with hot water jacket
A stirrer, a pH meter, a thermometer, and a reflux condenser were set in the reactor, and CaHPO 4 was charged inside with water, heated, and when the predetermined temperature was reached, CaCO 3 10 was added with a separate stirrer. Containing ~25 mol% Ca
10% Ca(OH) 2 + CaCO 3 preheated by a hot water jacket from a mixing tank of (OH) 2 and CaCO 3
The mixed solution was supplied to the reactor using a pump, and a reaction was carried out. After the reaction was completed, the product was filtered, washed with water, and dried. The reaction conditions and results are shown in Table 1. In addition, PH and Ca(OH) 2 + at each reaction time in Examples 1 and 2
The relationship between the addition rate of CaCO 3 is shown in FIGS. 1 and 2, and the infrared absorption spectrum pattern of the obtained product is shown in FIGS. 3 and 4. Both Figures 3 and 4 show a unique absorption related to carbonic acid at a wave number of around 1400 cm -1 .
It was confirmed that it contained carbonic acid. Comparative Example 1 CaHPO 4 and CaCO 3 were mixed in a ball mill, placed in a crucible, and fired in an electric furnace at 1000 to 1100°C under steam pressure for 5 hours. The first result is shown below.
【表】【table】
本発明方法は、温和な反応条件で短時間に容易
にHAPが製造でき、また高価な反応装置等も必
要とせず極めて経済的に有利な方法である。
本発明によつて得られる炭酸を含んだヒドロキ
シアパタイトは、極めて生体の骨や歯と組成的に
近いことから、生体親和性等において優れてお
り、人工骨、人工歯根に適した材料である。
The method of the present invention allows HAP to be easily produced in a short time under mild reaction conditions, and does not require expensive reaction equipment, making it an extremely economically advantageous method. Since the carbonic acid-containing hydroxyapatite obtained by the present invention has a composition extremely similar to that of living bones and teeth, it has excellent biocompatibility and is a suitable material for artificial bones and artificial tooth roots.
第１図、第２図はそれぞれ実施例１、２におけ
る各反応時間でのPHとCa（OH）2＋CaCO3の添加
率の関係を示すグラフである。第３図、第４図は
それぞれ実施例１、２で得られた生成物の赤外吸
収スペクトルのパターンである。
FIGS. 1 and 2 are graphs showing the relationship between PH and the addition rate of Ca(OH) 2 +CaCO 3 at each reaction time in Examples 1 and 2, respectively. FIGS. 3 and 4 are infrared absorption spectrum patterns of the products obtained in Examples 1 and 2, respectively.
Claims (1)
％含有するCa（OH）2とCaCO3との混合物をPH10
以下に保ちながら加え60〜100℃にて反応をおこ
なわせることを特徴とする炭酸含有ヒドロキシア
パタイトの製造法。1 A mixture of Ca( OH ) 2 and CaCO3 containing 2-25 mol% of CaCO3 in a slurry of CaHPO4 and water at PH10
A method for producing carbonic acid-containing hydroxyapatite, characterized by carrying out the reaction at 60 to 100°C while maintaining the temperature below.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27207184A JPS61151011A (en) | 1984-12-25 | 1984-12-25 | Production of carbonic acid-containing hydroxy apatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27207184A JPS61151011A (en) | 1984-12-25 | 1984-12-25 | Production of carbonic acid-containing hydroxy apatite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61151011A JPS61151011A (en) | 1986-07-09 |
| JPH0324406B2 true JPH0324406B2 (en) | 1991-04-03 |
Family
ID=17508687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27207184A Granted JPS61151011A (en) | 1984-12-25 | 1984-12-25 | Production of carbonic acid-containing hydroxy apatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61151011A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62223010A (en) * | 1986-03-25 | 1987-10-01 | Taihei Kagaku Sangyo Kk | Production of hydroxyapatite |
| JPS63225509A (en) * | 1987-03-13 | 1988-09-20 | Natl Inst For Res In Inorg Mater | Production of carbonate apatite powder |
| FR2869893B1 (en) * | 2004-05-06 | 2006-07-28 | Rhodia Chimie Sa | NOVEL CALCIUM PHOSPHATE GRANULES OF THE HYDROXYAPATITE TYPE, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS |
-
1984
- 1984-12-25 JP JP27207184A patent/JPS61151011A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61151011A (en) | 1986-07-09 |
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